Process for dyeing polyester textile materials with substituted anthraquinone dyestuffs



United States Patent Oflice 3,39%,947 Patented July 2, 1968 3,390,947 PROCESS FGR DYEING POLYESTER TEXTILE MATERIALS WITH SUBSTITUTED ANTHRA- QUINONE DYESTUFFS John H. Shown, Westfield, Paul A. Studer, Springfield,

and Albert M. Vajda, Cranford, N.J., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed June 24, 1964, Ser. No. 377,485 18 Claims. (Cl. 8-39) ABSTRACT OF THE DISCLOSURE A process for dyeing a polyester textile material, which process comprises contacting said textile material with a dye path containing a dyestufi comprising the reaction product of l,2,4-trihydroxy-anthraquinone, and a carbocyclic amine of the formula RNH wherein R is an aryl or cycloalkyl radical.

The present invention relates to a method for dyeing polyester fibers, and more specifically to a method for dyeing polyester fibers with particular water-insoluble dyestuffs which are the reaction products of purpurin, i.e., 1,2,4-trihydroxyanthraquinone. and a carbocyclic amine.

As is well known, polyester fibers such as those formed of polymeric reaction products of terephthalic acid and polyhydric alcohols have little or no affinity for dyestuffs normally employed for dyeing natural fibers. Furthermore, most dyestuffs proposed for utilization in dyeing such polyesters are not completely suitable in providing dyed articles displaying excellent sublimation and crocking properties, color fastness to light, heat, gases, dry cleaning agents, alkalies, perspiration and similar agents encountered in the normal preparation, use, wear, handling and/or washing of the dyed articles. Dyestuifs previously proposed for use in dyeing polyesters particularly have not been characterized by satisfactory sublimation properties and thus have not been adapted for utilization in dyeing techniques advantageously involving a thermofixation process.

Thus, it is recognized that a need exists for providing dyestuffs which are characterized by an ability to satisfactorily dye polyester fibers which are stable and which broaden the color range of suitable dyes available to the dye consumer.

Accordingly, it is the primary object of the present invention to provide a method for dyeing polyesters which provides colored articles having excellent color stability.

It is another object of the present invention to provide a method for dyeing a polyester fiber to a deep shade to provide a colored article which advantageously displays excellent color fastness when subjected to the conditions ordinarily encountered in the dyeing, use, wear, handling and washing of the colored article.

It is a particular object of the present invention to provide a method for dyeing a polyester fiber wherein a deep shade, such as black, navy blue to violet, maroon, or reddish-brown, is imparted to the fiber and the resultant fiber is characterized by excellent sublimation properties, excellent strength and fastness to light, heat, water, alkali, and the like agents ordinarily encountered in the dyeing, use, wear, handling, and/ or washing of the dyed fibers.

Broadly described, the present invention provides a method for dyeing a textile material which comprises contacting said textile material with a dye bath containing a dyestuff which is the reaction product of 1,2,4-trihydroxy-anthraquinone and a carbocyclic amine having the formula RNH wherein R is selected from the group consisting of aryl having no more than two benzene nuclei,

cycloalkyl having from 3 to 6 carbon atoms, and substituted derivatives of said aryl and cycloalkyl, wherein the substituents substituted therein are selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, sulfamyl, lower alkyl monoand di-substitutecl suliamyl, and heterocyclic radical-containing sulfarnyl, i.e. N-morpholinosulfamyl, N-piperidinosulfamyl, etc.

The products of the reaction between purpurin and carbocyclic amines, such as aromatic amines, are known compounds as exemplified by British Patent No. 23,927; French Patent No. 243,315; German Patents Nos. 84,- 505 and 86,150; Lubs, Chemistry of Synthetic Dyes and Pigments, p. 407 and Venkataraman, The Chemistry of Synthetic Dyes, p. 851, wherein such reaction products are disclosed as being precursors of sulfonated derivatives prepared therefrom which are suitable as dyestuffs. The exact structure of the reaction products of purpurin and carbocyclic amines employed in the present method is not known. For example, the German patents disclose reaction products prepared by condensing one mole of purpurin with each one and two moles of the aromatic amine and do not show structural formulas for the reaction products. It is recognized that the reaction of purpurin with an aromatic amine such as aniline yields a mixture of compounds. Venkataraman comments that in this reaction the fi-hydroxyl and one of the a-hydroxyls are replaced by amines, thus indicating that the mixture could be represented by the formulas:

and

On the other hand, Lubs states that the product was formerly believed to be a mixture of products of the above formulas but is now considered to be a mixture of compounds represented by the formulas:

and

Consequently, it will be understood that the phrase reaction product of 1,2,4-trihydroxy-anthraquinone (or purpurin) with a carbocyclic amine is intended to refer to such known compounds resulting from the condensation of one mole of purpurin with one mole of the carbocyclic amine, known compounds resulting from the condensation of one mole of purpurin with two moles of carbocyclic amine, and mixtures thereof. More specifically, such materials may be represented by the formula wherein R is as defined above and n is a number ranging from 1 to 2. It will be understood that reaction products of purpurin and a carbocyclic amine containing a mixture of monoand di-substituted purp-urin contemplated for utilization in the present method are characterized by a formula wherein n is mixed number between 1 and 2.

The dyestuffs employed in the method of the present invention exhibit excellent affinity for polyesters. In the present method, polyesters easily and satisfactorily may be dyed to relatively deep shades which vary widely in color depending upon the selection of the carbocyclic amine utilized in the preparation thereof to provide the radical R of the above-listed formula. By means of the invention, strong, stable dyeing of a black, navy blue, violet, maroon, or reddish-brown color can be imparted to polyesters. Moreover, due to the excellent sublimation properties of the dyestuffs employed in the present invention, the dyestuffs advantageously are adapted for use in embodiments of the invention wherein dyeing is carried out utilizing a relatively high temperature thermo-fixation technique.

The dyestuffs employed in the present invention suitably may be prepared by reacting purpurin with a particular selected carbocyclic amine at Widely varying temperatures, usually from about 100 to about 180 C., according to the above-mentioned known techniques. The reaction is allowed to continue for a time period requisite to obtain the desired shade of dyestuif. The shade of the dyestuff obtained may, and usually does, vary depending upon the temperature and reaction time employed, probably due to the formation of mixtures of reaction products containing varying proportions of monoand di-substituted purpurin products. The temperatures preferred for use are in the range of from about 140 to about 165 C.

Specific examples of dyestuffs contemplated for utilization include, inter alia, those prepared by the reaction of purpurin with cyclopropyl amine, cyclobutyl amine, cyclopentyl amine, cyclohexyl amine, methylcyclopropyl amine, chlorocyclopropyl amine, nitrocyclopropyl amine, bromocyclobutyl amine, iodocyclobutyl amine, 2-chlorocyclohexyl amine, 3-chlorocyclohexyl amine, 4-methoxycyclohexyl amine, 4-ethoxycyclohexyl amine, 4-butoxycyclohexyl amine, 3-nitrocyclohexyl amine, 2,5-clichlorocyclohexyl amine, 2,3-dibromocyclohexyl amine, 4-methylcyclohexyl amine, 3,5-dimethylcyclohexyl amine, 3-chloro- S-nitro-cyclohexyl amine, 2-chloro-5-methoxy-cyclohexyl amine, aniline, p-anisidine, p-toluidine, m-xylidine, mchloroaniline, m-bromoaniline, o-chloroaniline, o-bromoaniline, m-iodoaniline, p-chloroaniline, p-bromoaniline, pethoxyaniline, p-propoxyaniline, p-butoxyaniline, m-nitroaniline, 2,3-dichloroaniline, 2,5-dichloroaniline, 2,5-dibromoaniline, 3,5-diethylaniline, 3-ohloro-5-nitroaniline, 2- chloro 5 methoxyaniline, l-naphthylamine, 2-naphthyl amine, 4 chloro 1 naphthylamine, 3 nitro-l-naphthylamine, 4-methyl-1-naphthylamine, and 4-methoXy-2-naphthylamine. The dyestuffs prepared from purpurin and cyclohexylamine, aniline and the above-described alkyl, alkoxy, halo and nitro substituted amine derivatives thereof constitute the preferred dyestuffs for use in the present method.

In accordance with the method of the present invention, polyester articles are dyed with the above-described dyestuffs by contacting the articles with an aqueous dye bath containing the dyestuffs. Preferably the contacting is carried out by immersing the article in the dyebath. In certain preferred embodiments of the present method a carrier and a surface-active agent which functions as a dispersing agent also are employed in the dyebath. Specific examples of such carriers include, Without limitation, methyl salicylate and ortho-phenylphenol. The latter may be added to the dyebath in the form of the sodium salt of ortho-phenylphenol along with equivalent amounts of diammonium phosphate which converts the sodium salt into the phenylphenol in situ.

An alternate method of dyeing the fiber With the dyestuff entails contacting the polyester fiber with the dyestuff solution and subsequently dyeing in pressurized machines at temperatures ranging up to about 125 C.

A preferred method of dyeing the fiber with the dye stuff is by means of the Thermosol process wherein the fiber is padded with a dispersion of the dyestuff, dried and subjected to a temperature of 190 to 230 C. for about /2 to 1 minute. It is in the exercise of this method of dyeing that sublimation fastness is very important, and the fact that the instant dyes have excellent sublimation fastness accounts for their value.

The method of the invention contemplates the utilization of any surface-active agent conventionally employed for providing dyestuif and/or dyestulf-carrier dispersions for dyeing polyesters. Such surface-active agents generally are nonionic, anionic or mixtures thereof. Specific examples of such surface-active agents include water-soluble ligninsulfonates, i.e., the sodium, calcium, and magnesium salts of ligninsulfonic acids and partly disulfonated ligninsulfonic acids such as those disclosed in US. Patent No. 2,371,136; alkyl naphthalene sulfonates, e.g., the sodium, potassium, and ammonium salts of monoand di-propyl and butyl-naphthalene sulfonates; alkali metal fatty sulfates, such as sodium lauryl sulfate, sodium tridecyl sulfate and sodium tallow sulfate; alkali metal salts of alkyl sulfosuccinates, such as sodium dioctyl sulfosuccinate; alkali metal alkyl aryl sulfonates, such as sodium nonyl benzene sulfonate; ethylene oxide ethers of alkyl phenols, such as nonylphenol polyoxyethylene ethers; ethylene oxide ethers of fatty alcohols, such as tridecyl alcohol polyoxyethylene ethers; ethylene oxide ethers of alkyl mercaptans, such as dodecyl mercaptan polyoxyethylene thioethers; ethylene oxide esters of fatty acids, such as the condensation products of lauric acid and polyethylene glycols; ethylene oxide condensation products of fatty amides, such as lauramide; and condensation products of ethylene oxide with partial fatty acid esters of polyhydric alcohols, such as polyoxyethylene ethers of lauric acid partial esters of sorbitol; and the like.

In accordance with the method of dyeing polyester fibers with the instant dyes, a wide range of temperatures may be utilized. When ordinary dyeing methods at atmospheric pressure are employed, temperatures above room temperature usually are employed, preferably ranging from about C. to the boil. Better results are obtained when dyeing is carried out at higher temperatures such as would prevail in a pressure vessel. In dyeing in a pressure vessel temperatures up to about C. are employed. Still better results are obtained when the Thermosol process is employed wherein the temperatures range usually is from about to about 230 C., with preferred results being obtained in the range of from about 210 to about 220 C.

The amount of the dyestuif employed in the dyebath in accordance with the present invention may vary widely. The amount usually employed in embodiments of the invention wherein the dyeing is effected by immersing the fabric into hot dyebaths is in the range of from about 0.01 to about 15 parts by weight, preferably from about 0.1 to about 10 parts by weight, per 100 parts water in the dyebath. In embodiments of the invention wherein the Thermosol dyeing technique is employed, greater proportions of dyestuff to water suitably may be employed,

5 and preferably the dyebath utilized is in the form of a dispersion of the dyestuff.

The contacting of the present method is carried out over a time period requisite to provide the desired build-up of dyestuff, as evidenced by the color depth of the dyed article to be obtained. At the above-indicated preferred temperatures and dye concentrations, the time periods normally required are in the range of from a few minutes to about 3 hours.

It is understood that the actual temperature and time period employed in a given embodiment of the invention will vary depending upon, inter alia, the dyeing technique employed, the particular nature and amounts of polyesters and dyestuff employed, and the desired color depth of the final dyed product, as Well as the particular carrier and surface-active agent, if any, utilized.

Following the contacting step, the dyed article suitably may be rinsed and dried in any conventional manner.

The present method contemplates dyeing polyesters broadly. The particular polyesters most commonly utilized are the polyesters of terephthalic acid and aliphatic and aromatic polyhydric alcohols, e.'g., ethylene glycol, propylene glycol, glycerine, p-xylene glycol and the like.

The method of the invention having been described above in detail, the following examples are presented to show specific embodiments thereof. It will be understood that the examples are given merely for illustration purposes and not by way of limitation.

Example 1 150 parts of p-anisidine were melted in a flask and a mixture of 10 parts boric acid and 32 parts purpurin were then added thereto. The reactant mixture was heated to 150 C. in two hours and then held for six hours at this temperature. The resultant reaction mixture was then cooled to 6570 C., diluted with 150 parts of ethanol, and filtered at 6570 C. to separate the solid dyestufi" which was then washed with 250 parts of ethanol.

The product filter cake Was then resludged in 500 parts of Water and 50 parts of 20 B. hydrochloric acid and subsequently refiltered to remove excess anisidine. The navy-blue colored filter cake obtained contained dyestuff product equivalent to 36- parts of dry dye, a mixture of dyes having the formulas 14 2) OH(NHC H OCH 2 and C14H5O2(OH2)Z(NHCGH4OCH3), the 01- mer predominating.

A dyebath of the above-described dyestuff was formed by initially mixing about 1 cc. of a aqueous solution of Aviton T, a sodium hydrocarbon sulfonate, with stirring, into 100 cc. of water at 54 C. About cc. of each of a 10% aqueous solution of diarnmonium phosphate and a 10% aqueous solution of sodium phenyl phenolate were then introduced, with stirring, into the resulting mixture. A dispersion of about 1 gram of the dyestuff pasted in 10 cc. of a 10% aqueous solution of Aviton T was then mixed with the phosphate-containing mixture and the resultant mixture was then diluted with water to 300 cc.

A sample of poly glycol terephthalate (Dacron) fabric was then immersed in the dyebath, and the dyebath was heated to boiling. The fabric was maintained in the boiling dyebath for about 1 hour. At the end of this period the fabric was removed from the dyebath, immersed in a boiling 0.1% soap solution for about 5 minutes, thereafter rinsed with water, and then dried.

The dyeing thereby obtained had an even, intense navy blue color approaching a bluish black in hue and the dyed fabric displayed excellent sublimation properties and excellent fastness to heat, light, washing and crocking.

Example 2 The procedure of Example 1 was repeated with the exception of substituting m-chloroaniline for p-anisidine.

6 A reddish-brown dyestutf was obtained, a mixture of products of the formulas (C H O )OH(NHC H CI) and C H 0 (OH )--(NHC H Cl), with the former predominating.

A dyebath of the above-described dyestutf Was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

The dyed fabric obtained had an even, intense reddish-brown color and was characterized by excellent sublimation properties, and excellent fastness to light, heat, washing, and crocking.

Example 3 Example 4 The procedure of Example 1 was repeated with the exception of substituting p-toluidine for p-anisidine. The

dyestuff obtained was characterized by a strong navy blue color and was a mixture of products of the formulas (C14H5'O2) and With the former predominating.

A dyebath of the above-described dyestuif was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

The dyed fabric thereby obtained was observed to have an intense, deep navy blue color, excellent sublimation characteristics, and fastness to heat, light, washing and crocking.

Example 5 The procedure of Example 1 was repeated with the exception of substituting m-xylidine for p-anisidine. The dyestulf obtained was characterized by a strong navy blue color and was a mixture of products of the formulas (C14H5O2) 2 and 14 5 2( )2-( s a 3 a) with the former predominating.

A dyebath of the above-described dyestuif was prepared and a sample of Dacron fabric was dyed therewith in accordance with the procedure of Example 1.

The dyed fabric thereby obtained was observed to have an even, intense navy blue color, excellent sublimation characteristics and fastness to heat, light, washing and crocking.

Example 6 The procedure of Example 1 was repeated with the exception of substituting o-chloroaniline for p-anisidine. The dyestuif obtained was characterized by a deep maroon color and was a mixture of products of the formu- 121$) and With the former predominating.

A dye-bath of the above-described dyestulf was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

The dyed fabric thereby obtained was observed to have an even, intense maroon color, excellent sublimation characteristics and fastness to heat, light, washing and crocking.

Example7 The procedure of Example 1 was repeated with the exception of substituting p-chloroaniline for p-anisidine. The dyestutf thereby obtained was characterized by a violet color and was a mixture of products of the formulds and 14 2( )2( 6 4 with the former predominating.

A dyebath of the above-described dyestutf was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

The dyed fabric thereby Obtained was observed to have an even, dull violet color, excellent sublimation characteristics, and fastness to heat, light, washing and crockmg.

Example 8 The procedure of Example 1 was repeated with the exception of substituting 2,5-dichloroaniline for p-anisidine. The dyestulf obtained was characterized by a strong reddish-brown color and was a mixture of products of the formulas (C H O )OH(NHC H Cl and C H O (OH) (NHC H Cl with the former predominating.

A dyebath of the above-described dyestuff was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

The dyed fabric thereby obtained was observed to have an even, intense reddish-brown color, excellent sublimation characteristics, and fastness to heat, light, washing and crocking.

Example 9 The procedure of Example 1 was repeated with the exception of substituting 2,3-dichloroaniline for p-anisidine. The dyestuff thereby obtained was colored a strong maroon and 'was a mixture of products of the formulas (C14H5O2) and 14 5 2( )2( s a 2) with the former predominating.

A dyebath of the above-described dyestuff was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

The dyed fabric thereby obtained was observed to have an even, intense maroon color, excellent sublimation characteristics, and fastness to heat, light, washing and crocking.

Example 10 The procedure of Example 1 was repeated with the exception of substituting 3-nitroaniline for panisidine. The dyestuif obtained was characterized by a strong maroon color and was a mixture of products of the formulas (CHI-I502) 2 and 14 s 2( )Z( G 4 Z) with the former predominating.

A dyebath of the above-described dyestuff was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

The dyeing thereby obtained had an even, intense maroon color, and the dyed fabric displayed excellent sublimation properties, and fastness to heat, light, washing and crocking.

Example 11 The procedure of Example 1 was repeated with the exception of substituting cyclohexylamine for p-anisidine. The dyestuif obtained was characterized by a reddishbrown color and was a mixture of products of the formu- 121$ (C14H5O2)OH(NHC4H11)2 and 14 5 Q( )2 G 11) with the former predominating.

A dyebath of the above-described dyestuff was prepared and a sample of Dacron fabric dyed therewith in accordance with the procedure of Example 1.

Example 12 22. g. of the dyestuff of Example 1, 20 g. of Polyfon H. a sodium ligninsulfonate, and 4 cc. of Nekal WS-25, a sodium alkylnaphthalene sulfonate, were wet down in a mixer with water to give a thick, doughy mass. The water was evaporated off to yield a viscous mixture, and the resultant mixture was viscous milled for 1 to 1 /2 hours with water being added as needed, the final water addi tion being sufiicient to provide a 20% by weight dispersed paste of the dyestuff.

Eight ounces of the dyestuif paste were dispersed in 83 cc. of warm water and poured into an aqueous solution containing 0.2 g. of Keltex gum, an alginic thickening agent, and 1 cc. of Nekal NF, a sodium alkyl naphthalene sulfonate. The resultant solution was diluted to a total volume of a gallon by the addition of water.

A Dacron fabric was padded with the dyestulf at about 70 (1., dried, and then cured at about 220 C. for seconds. The resultant dyed material was then soaped at the boiling point for 5 minutes, washed with water, and dried. An even, intense navy blue dyeing was obtained which had excellent sublimation, wash and crock-fastness properties and good fastness to light.

Example 13 The procedure of Example 12 was repeated with the exception of substituting, each in turn, the dyestuffs of Examples 2 and 11 for the dyestutf of Example 1.

In each case the dyed fabric was characterized by an even, intense dyeing of the above-disclosed respective colors of the dyestuifs. The dyed fabrics each advantageously displayed excellent sublimation, wash and crock fastness properties and good fastness to light.

While the above-described examples are limited to dyeing of polyesters, it will be understood that the present method also is applicable to the dyeing of textile materials formed of natural materials such as cotton, wool, and the like, and other synthetic fibers such as those formed of polyamides, polyvinyl compounds, cellulose acetate, viscose, and the like.

From the above description and examples various modifications will be apparent to those skilled in the art which do not depart from the scope of the process of the invention. Thus, it is intended that the invention be limited only by the scope of the appended claims.

What is claimed is:

1. A method for dyeing a polyester textile material which comprises contacting said textile material with a dye bath containing a dyestuff which is the reaction product of 1,2,4-trihydroxy-anthraquinone and a carbocyclic amine having the formula RNH wherein R is selected from the group consisting of cycloalkyl having from 3 to about 6 carbon atoms, aryl having no more than two benezene nuclei, and substituted derivatives of said cycloalkyl and aryl radicals, wherein the substituents substituted therein are selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, sulfamyl, and substituted sulfamyl groups.

2. The method according to claim 1 wherein said dye bath contains a dyestutf carrier and a surface-active agent as a dispersing agent.

3. The method according to claim 2 wherein said dyestuff carrier is selected .from the group consisting of methyl salicylate and ortho-phenylphenol and said surface-active agent is selected from the group consisting of anionic surface-active agents, nonionic surface-active agents, and mixtures thereof.

4. The method according to claim 1 wherein said contacting is carried out by immersing said textile material into said dyebath at a temperature in the range of from about 80 to about C.

5. The method according to claim 1 wherein said dyebath is in the form of a dispersion of said dyestuff, and subsequent to said contacting of said textile material with said dyestuff dispersion, the resultant dyestulf dispersioncontaining textile material is dried, and thereafter heated at a temperature in the range of from about 190 to about 230 C.

6. The method according to claim 1 wherein the amount of said dyestulf in said dyebath is in the range of 0.01 to about 15 parts by weight per 100 parts water in said bath.

7. The method according to claim 1 wherein said amine is p-anisidine.

8. The method according to claim 1 wherein said amine is o-anisidine.

9. The method according to claim 1 wherein said amine is p-toluidine.

10. The method according to claim 1 wherein said amine is m-Xylidine.

11. The method according to claim 1 wherein said amine is p-chloroaniline.

12. The method according to claim 1 wherein said amine is o-chloroaniline.

13. The method according to claim 1 wherein said amine is m-chloroaniline.

14. The method according to claim 1 wherein said amine is 2,5-dichloroaniline.

15. The method according to claim amine is 2,3-dichloroaniline.

16. The method according to claim amine is 3-nitroaniline.

17. The method according to claim amine is aniline.

18. The method according to claim amine is cyclohexylamine.

1 wherein said 1 wherein said 1 wherein said 1 wherein said References Cited UNITED STATES PATENTS OTHER REFERENCES K. Venkataraman, The Chemistry of Synthetic Dyes, vol. 2, 1952, pp. 850 and 851, publ. by Academic Press Inc., N. Y. City.

NORMAN G. TORCHIN, Primary Examiner.

T. I. HERBERT, Assistant Examiner. 

